Determining and Understanding N-H Bond Strengths in Synthetic Nitrogen Fixation Cycles

  • Máté J. Bezdek
  • Iraklis Pappas
  • Paul J. Chirik
Part of the Topics in Organometallic Chemistry book series (TOPORGAN, volume 60)


The fixation of atmospheric dinitrogen to ammonia using molecular catalysts has been a long-standing challenge in homogeneous catalysis and synthetic chemistry. New approaches to this problem may offer more energy-efficient and carbon-neutral routes to this important industrial compound. Despite the ubiquity of ammine, amide, imide and diazenide ligands in coordination chemistry, little thermodynamic data is available for understanding N-H bond strengths in molecules bearing these nitrogenous fragments. This article presents an overview of both computational and experimental approaches for the determination of N-H bond dissociation free energies in a variety of compounds relevant to nitrogen fixation to ammonia. The influence of metal oxidation state, ancillary ligand and identity of the nitrogen donor are highlighted. Implications for future design of molecular systems for the reduction of dinitrogen are discussed.


Ammonia Bond dissociation free energy Nitrogen fixation 


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Copyright information

© Springer International Publishing AG 2017

Authors and Affiliations

  • Máté J. Bezdek
    • 1
  • Iraklis Pappas
    • 1
  • Paul J. Chirik
    • 1
  1. 1.Department of ChemistryPrinceton UniversityPrincetonUSA

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